CA1137690A - Hydrolysis and microbe-resistant thermoplastically processable polyurethane elastomers, their manufacture and use as coating materials and molded parts - Google Patents
Hydrolysis and microbe-resistant thermoplastically processable polyurethane elastomers, their manufacture and use as coating materials and molded partsInfo
- Publication number
- CA1137690A CA1137690A CA000340275A CA340275A CA1137690A CA 1137690 A CA1137690 A CA 1137690A CA 000340275 A CA000340275 A CA 000340275A CA 340275 A CA340275 A CA 340275A CA 1137690 A CA1137690 A CA 1137690A
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- Prior art keywords
- polyurethane elastomers
- groups
- butanediol
- shore
- polyether polyols
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2250/00—Compositions for preparing crystalline polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
HYDROLYSIS AND MICROBE-RESISTANT THERMOPLASTICALLY
PROCESSABLE POLYURETHANE ELASTOMERS, THEIR MANUFACTURE
AND USE AS COATING MATERIALS AND MOLDED PARTS
Abstract of the Disclosure Polyurethane elastomers ranging in hardness degrees 60 Shore A to 75 Shore D are prepared by reacting polyols having at least 50 percent primary hydroxyl groups, chain extenders and organic diisocyanates in an NCO/OH ratio of 1.05:1 to 1.08:1. These elastomers are hydrolysis and microbe resistant and are thermoplastically processable.
PROCESSABLE POLYURETHANE ELASTOMERS, THEIR MANUFACTURE
AND USE AS COATING MATERIALS AND MOLDED PARTS
Abstract of the Disclosure Polyurethane elastomers ranging in hardness degrees 60 Shore A to 75 Shore D are prepared by reacting polyols having at least 50 percent primary hydroxyl groups, chain extenders and organic diisocyanates in an NCO/OH ratio of 1.05:1 to 1.08:1. These elastomers are hydrolysis and microbe resistant and are thermoplastically processable.
Description
~YDROLY5IS AND MICROBE-RESISTANT, THERMOPLASTICALLY
PROCESSABLE POLYURETHANE ELASTOMERS, THEIR MANUFACTURE
AND ~SE AS COATING MATERIALS AND MOLDED PARTS _ _ Background of the Invention 1. Field of the Inve_tion The invention relates to hydrolysis and microbe-xesistant thermoplastically processable urethane elastomers having hardness degrees of 60 Shore A ~o 75 Shore D produced by the reaction o primarily linear polyether polyols in which at least 50 percent of the 0~ groups are primary hydroxyl groups, chain extenders, and organic diisocyanates in a ratio ~f NCO groups to total hydroxyl grOL1pS of 1.05:1 to 1.0B:1 and optionally hydrQxyl group-containin~-polytetrahydrofurans or linear polyesters.
PROCESSABLE POLYURETHANE ELASTOMERS, THEIR MANUFACTURE
AND ~SE AS COATING MATERIALS AND MOLDED PARTS _ _ Background of the Invention 1. Field of the Inve_tion The invention relates to hydrolysis and microbe-xesistant thermoplastically processable urethane elastomers having hardness degrees of 60 Shore A ~o 75 Shore D produced by the reaction o primarily linear polyether polyols in which at least 50 percent of the 0~ groups are primary hydroxyl groups, chain extenders, and organic diisocyanates in a ratio ~f NCO groups to total hydroxyl grOL1pS of 1.05:1 to 1.0B:1 and optionally hydrQxyl group-containin~-polytetrahydrofurans or linear polyesters.
2. Prior Art ~ hermoplastically processable urethane elastomers based on primarily linear polyester polyols of aliphatic dicarboxylic acids and alkylene glycol~, hydroxy carboxylic acids, or of polyether polyols based on polytetrahydrofurans are knownO A survey of these polyurethane elastomers is describedr for in~tance, in ~Urethanes in Elastomer~ and Coatings~, Technomic Publishing Company, 256 West ~tate Street, Westport, Connecticut, U.S.A., 1973, pages 201 to 230, ~r in the Plastics ~andbook, Volume VII, Polyurethane~, by R.
Vieweg and El. Hoechtlen, Carl Hanser Pl:blishers, Munich, 1966 Pages 20b and the following.
In spite of the advantages concerning their mechani-cal ~tability and their wear behavior, polyurethane elastomers ~13~
based on polyester p~lyols also have some very negative properties. These products, unless stabilized or improved by suitable additives, are sensi~ive to hydrolytic decomposition or infestation and destruction by micro organisms. Further-more, the flexibility of these elastomers, particularly the hard formulations, leaves something to be desired at tempera-tures below ~reezing. For example, applications at low temperatures are not feasible because of the relatiYely high solidification temperatures of the elastomers which in turn depend on the chemical compositions and their hardness.
Compared with this, polyurethane elastomers based on polytetrahydrofurans have the advantage of greater hydrolysis resistance, resistance to micro organisms and flexibility even at low temperatures to minus 50C and below.
A disadvantage, howeverr is that the mechanical properties of these products can be varied only within narrow limits because in principle only the molecular weight of the polytetrahydrofuran can be changed and that the production oosts of these products are relatively high.
It seemed appropriate to also use other poly-oxyalkylene glycols for the manufacture of polyurethane elastomers instead of the hydroxyl group-containing polytetra-hydrofurans. In many cases, howeYer, the reaction of polyoxy-alkylene glycols with polyisocyanates in the one-stage process takes place so slowly, even in the presence of catalysts, that an economically desirable process is not feasible. Only by means of polyoxyalkylene polyol polyisocyanate prepolymers, ~376~1~
which are ~ubsequently reacted with ~hain extenders, can the desired end product be obtained in a reas~nable and control-1 able manne r .
Using the prepolymer stage, however, means a rela-tively higher equipment requirement compared with the ~ingle-~tage process. In addition to the already required storage capacities for the p~lyoxyalkylene polyol and the polyiso-cyanate, the prepolymer process, contrary to the single-step process, requires equipment for the manufacture of the pre-polymer, and sufficient storage capacity for the completedprepolymer, while the formulation is being adjusted which is generally required for reliable processing into a high-quality elastomer. Furthermore, the requirements of mixing e~uipment for the reaction of the prepolymer and chain extenders under certain circumstances can vary greatly due to their viscosity and the quantities employed. It is also known that pure polyether polyols can be stored for an extended period of time contrary to isocyanate prepolymers which, at temperatures up to 80-C, are difficult to ~tore and can only, under certain circumstances, with the aid of 6uitable a~ditives, be main-tained constant with respect to the viscosity and reactivity for a sufficiently long period of time~
The purpose of this invention is to manufacture from inexpensive, easily obtainable raw materialx empl~ying a technically ~imple process, polyurethane elastomers having high resistance against micro organis~s and good mechanical 1:~3~71 i9~
properties, particularly at temperatures below the freezing point.
Surprisingl~, it was found that thermoplastically, easily processable polyurethane elastomers with good mechanical properties and excellent hydrolysis and microbe-resistance can be produced from higher molecular weight polyoxyalkylene polyols, quickly and in a simple manner in a single-stage reaction. Polyoxyalkylene polyols having primary hydroxyl groups are reacted either alone or in mixtures, with certain polyether polyols or polyester polyols, with polyisocyanates, particularly aromatic diisocyanates, chain extenders, possibly in the presence of catalysts, or other additives. The accurate maintenance of a narrow range of the WCO/OH ratio is the determining factor for obtaining good mechanical properties. Surprisingly, this is successful in spite of the known, hi.gh monofunctional contents of such polyether diols which may amount to 10 percent by weight and more.
In particular the present invention provides hydrolysis and microbe-resistant thermoplasticly processable polyurethane elastomers having hardness degrees of 60 Shore A
to 75 Shore D which are obtained by a one shot process comprising reacting A) primarily linear polyether polyols having molecular weights of 500 to 10,000 in which at least 50 percent of the OH groups are primary hydroxyl groups or B) mixtures of such polyether polyols ~A) with hydroxyl group containing polytetrahydrofuran and/or primarily linear polyester polyols, C) low molecular weight linear chain extenders, and D~ organic diisocyanates wherein the ratio of NCO groups to hydroxyl groups of compo-,;s..~.
~L376~
nents (A) or ~B) and (C) is 1005:1 to 1.08:1.
In another aspect the present invention provides a one shot process for the manufacture of hydrolysis and microbe-resistant thermoplasti.cally processable polyurethane elastomers havlng hardness degrees of 60 Shore A to 75 Shore D wherein A) primarily linear polyether polyols with molecular weights of 500 to 10,000 in which at least 50 pèrcent of the OH groups are primary hydroxyl groups or s) mixtures of such polyether polyols (A) with hydroxyl group containing polytetrahydrofuran and/or primarily linear polyester polyols C) low molecular linear chain exterders and D) organic diisocyanates are reacted at temperatures of 20 to 250C is such quantities -that the ratio of the NCO groups to the hydroxyl groups of components (A) or (B) and (C) is 1.05 to 1.08:'.
Description of the Preferxed Embodiments Hydrolysis- and microbe-resistant thermoplastically - 20 processable polyurethane elastomers having hardness degrees of 60 Shore A to 75 Shore D are-obtained by the reaction of A) primarily linear polyether polyols having molecular weights of 500 to 10,000 in which at least 50 percent of the 0~ groups are primary hydroxyl groups or, .
: ~.
~ a -7~
B) mixtures of such polyether polyols (A) with hydroxyl group-containing polytetrah~drofurans and/or primarily linear polyester polyols, C~ low molecular, linear chain extenders, and D) organic diisocyanatesg These raw materials are reacted employing the one-shot process, possibly in the presence of catalysts and auxiliaries, in such quantities that the ratio of NCO groups to hydroxyl groups in the starting components (A) or ~B) and ~C) is 1.05:1 to 1.08:1.
The molar ratios between polyether polyol (A) or the mixtures (B) of polyether polyol (A) and polytetrahydrofuran and/or polyester polyol and chain extender (C) may be varied within ~ide limits. Depending upon the desired hardness of the polyurethane elastomer, the ratio of polyol to chain extender can vary from about 1.0~ D5 to approximately 1.0:1.0, preferably from 1~0: 09 08 to 1.0;0.8. The quantity of the chain extender employed is also a function o the molecular weight of the polyether polyol ~A) or the mixture (B~.
Those polyethers polyols contemplated for the manufa~ture of the polyurethane elastomers according to this invention, are those polyether pvlyols (A~ which are primarily linear, that is di~unctional, of molecular weight ranges of 500 to 10~000r preferably o~ 600 to 6,000, and in which at least 50 percent, preferably 60 to 80 percent, of the OH
groups are primary hydroxyl groups~ Particularly suited a~
polyether polyols are the condensation products of ethylene ~5-. ~3~
oxide, propylene oxide, 1,2 butylene oxide, tetrahydrofuran, epichlorohydrin~ and styrene oxide with s~arter molecules, preferably those starter molecules containing 2 active hydrogen atoms. Suitable starter molecules include: water, N-alkyldiethanolamines having 1 to 4 carbon atoms in the alkyl radi~al such as N-methyl-diethanolamine and preferably, aliphatic diol~, parti~ularly those having 2 to 6 carbon atoms su~h as ethylene glycol, propylene slycol, 1,4-butanediol and 1,6-hexanediol. Mixtures of starter molecules may al o be used if desired.
For the manufacture of the polyether polyols (A~, the alkylene oxides may be reacted in mixtures, in blocks, or ~equentially in blocks with the stipulation that the end product contains at least 50 percent primary hydroxyl groups.
Preferably used are those polyether polyols of propylene oxide and ethylene oxide where at least part of the ethylene oxide i~ arranged as a terminal block.
Such polyether polyols may be obtained, for instance, by initially condensing the propylene oxide with the starter molecules followed by the addition of ethylene oxide~ or by initially condensing all of the propylene oxide as a mixture with part of the ethylene oxide and subseguently condensing the remainder of the ethylene oxide~ or by initially condens-ing past of the ethylene oxide~ then the entire propylene oxide, followed by condensing the re~t of the ethylene oxide with the starter moleculeO
. ~3769~
Polypropylene glycols which have been terminated with tetrahydrofurans have proven to wor~ well ~nd are there fore preferred.
The polyether polyols (A) may be used individually as well as in mixture~. They may be mixed with hydroxyl group-containing polytetrahydrofurans having molec~lar weights of 500 to 6000, preferably of 600 to 3000, and/or with primar-ily linear polyester polyols having molecular wieghts of 500 to 4500, preferably 600 to 3000. Mixtures (B) of polyether polyols (A) and hydroxyl group-con~aining polytetrahydrofurans and/or polyester polyols containing more than 50 percent by weight, preferably 60 to 99 percent by weight of polyether polyols based on the total weight of polyether polyols have proven to work particularly well.
The process for the preparation of hydroxyl group-containing polytetrahydrofurans is well known. Products produced by the polymerization of tetrahydrofuran in the presence of acetic anhydride with antimony pentachloride as a c~talyst and subsequent transesterification have proven to work particularly well~
Suitable primarily linear polyester polyols are obtained (1) by the polymerization of caprolactones, prefer-ably epsilon-caprolactone, (2) by the polycondensation of omega-hydroxy-carboxylic acids, or (3) by the reaction of aliphatic dicarboxylic acids having 4 to 6 carbon atoms, e.g~, 6uccinic acid, glutaric acid and adipic acid, with aliphatic glycols having 2 to 6 carbon atoms, such as 1,6-hexanediol~
. ~IL3~69~ -and preferably 17 4-butanediol and ethylen~ glycol . Polyester polyols preferably used for the manufacture of the poly- -urethane elastomers according to this invention include hydroxyl group-containing caprolactones and adipates of adipic acid with 1~4-bu~anediol, mixtures of i~4-butanediol and ethylene glycol, or 1,6-hexanediol in a mole ratio of 4:1 to 1:4, preferably 1:1.
The low molecular linear chain extenders employed have molecular weights of less than 500, preferably of 60 to 300. Suitable substances include aliphatic diols ~ith 2 to 12 carbon atoms and particularly, those with an even number of carbon atoms, esters of terephthalic acid with glycols having 2 to 4 carbon atoms, and hydroxyalkylene ether of hydroquinone.
Examples of these include: ethylene glycol, 1,4-butanediol, 1,6-hexanediol, terephthalic acid-bis-ethylene glycol, or 1,4-butylene diglycol and 1,4-di-(beta-hydroxyethyl)-hydro quinone with 1,4-butanediol having been proven ~o work particularly well.
Suitable organic diisocyanate~ (D~ for the manufac-ture of the polyurethane elastomers according to thi& inven-tion are cycloaliphatic, aliphatic and, preferably, aromatic diisocyanates. These include: cycloaliphatic diisocyanates ~uch as 1,4-cyclohexane diisocyanate~ 4,~'-diisocyanato di~y~lohexylmethane, or i~ophorone diisocyanate; aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate~ and aromatic diisocyanates such as diphenyl diisocyanate, m- or p-phenylene diîsocyanate, 2,4- ana 2,6-toluene diisocyanate or ~ ~376g~
their i~omer mixtures; ~,2'-, 4,47-~ 2,~ diphenylmethane diisocyanate or their ~omer mixtures, andlpreferably, 4.4'~
diphenylmethane dii~ocyanate.
As previously mentioned9 lt i~ an imp~rtant facet of thi~ $nvention that, in order to obtain polyurethane elastomer~
with good mechanical properties, ~he ~arting camponent~ ~A~
to (D) are reac~ed in a narrow NCO/O~ ratio. According to the invention~ the st~rting c~mponents are reacted in such quanti ties that the ratio of NCO groups of the diisocyanates ~D) to the ~um of the hydroxyl groups of the component (A~ or (B) and (C) i~ 1.05:1 to 1.08:1, preferably 1~07:1. The ratio of NCO
to OH groups must be maintained in spi te of the varying ratios of components (A) or (~). A slight drop below this NCO/OH
ratio can very ~uickly result ~n crumbly, mechanically worth less materials. ~xceeding ~he value!s can result in products which have unstable storage properti.es which are partially insoluble in solven~s, which cont~in swelling materials and which are thus difficult or no longer processable in a thermo-plastic manner because of he vi~cosity which "after develops"
20 over an extended period of time.
The polyurethane elastomers according to thi~ inven-tion can be produced according to the one-shot process, in the presence of catalyst~, in a batch-type manner, ~r prefer-ably in a continuous manner wherein the reaction mixture i~
carried on ~ continuous circulating band after ~uitable metering and mixing of the ~tarting components at tempera~ures of 20 to 150-C, preferably S0 to 130~C~ On the circulating _g_ ~..
. ~37~9~
band, the reaction mixture goes ~hrough a temperature profile, first to 100 ~o 250C, then dropping to 20~C to ~00C as a result of exothermal reaction. ~he reaction mixture is removed and urther proeessed after solidifying in plates, or it can be ~ed directly to a conveyor granulator as an endless thick plate.
In addition to this, the single-stage reaction may also be conducted in a ~o called reaction extruder.
Suitable catalysts which accelerate the reaction between the NC0 groups of the isocyanates and the hydroxyl groups of components (A) or (B) and ~C) are the tertiary amines well known to those skilled in the art. These include triethylamine, dimethylcyclohexylamine, N-methylmorpholin~r N,NI-dimethylpyrazine, diazabicyclo~-(2,2,2)-octane and similar materials as well as organic metal compoullds such as titanic esters, iron compounds such as iron acetylacetonate, tin diacetate, tin dioctoate, tin dilaurate, or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetatet dibutyltin dilaurate, or ~imilar materials. m e 20 catalysts are normally used in quantities of 0.001 to û.l p~rt per 100 parts of polyether polyols ~A) or mixture (B~ If desired, the catalyst can be eliminated.
In addition to catalysts, other additives may also be incorporated in the reaction components without detriment~
These incl~de inhibitorst stabilizers with respect to light, heat or discolora'Lion, dye~, color pigments, inorganic and orgarlic filler~.
~37~9~
The polyurethane elastomers produced according to the instant invention have hardness ~egrees of 60 Shore A to 75 ~hore D~ show good hydrolysis resistance, very good resist-ance to the infestation of micro organisms and have excellent mechanical properties.
Depending upon their chemical compo~ition, the p~lyurethane elastomers are transparent or opaque and generally have a high crystallini~y~ They can, therefore, be processed correspondingly well into, hoses, hollow parts, foils, and melt-coatings according to the collander, spray injection~
extrusion, and blowing processes. ~hey are soluble in ~uit-able organic solvents such as dimethyl formamide without undergoing swelling and thus, suitable for textile coatingsO
As a result of the very pronounced incompatibility between the rigid segment and the amorphous range, unusually low freezing temperatures of minus 50C and below, and good ther~al stabilities of 150C and above are obtained even with high hardness degrees of, for instance, 63 Shore D.
The following Examples are intended to illustrate the nature o~ ~he inYention. Unless otherwise stated, the parts and percentages are by weight.
1~--. ~IL37~
Example 1 General Process Inst_uctions:
A stipulated am~unt of a polyoxyalkylene diol with a polypropylene oxide chain and terminal primary hydroxyl groups or a mixture of such a polyoxyalkylene diol with othex polyols and polytetrahydrofuran diols or polyester polyols is heated - to 80 to 120C while being stirred vigorously. An amount of 1,4-butanediol corresponding with the desired NCO/OH ratio and required for the desired degree of hardness of the resulting polyurethane elastomer is added. As the chain extender is added the temperature of the mixture drops by approximately 20C. After mixing for approximately one minute, the cal~
~ulated ~uantity of 4,4'-diphenylmethane diisocyanate in the form of flakes is added whereupon the temperature of the re-action mass initially drops to about 40 to 60C and sub-sequently quickly begins to increase and can reach tempera-tures up to 180~C and more within a few minutes. Before the reaction mixture solidifies, approximately upon passing ~hrough the 100~C mark, a ~hin layer of ~.he reaction mass is poured in~o molds which are heated to 100 to 130C and where the exothermal polyaddition reaction is completed with~n a sh~rt period of time. The unmolded panels are tempered at B0 to 100C ~or 15 hours, are subsequently crushed and are sprayed onto samples.
Liquid 4,4'-diphenylmethane diisocyanate is pre~er-ably employed in a continuous process. 5uitable catalysts and stabilizexs may also be employedl ~37~
An elas~omer was prepared via the general process instructions empls~ying the following:
5ûO parts of a pc lypropylene glycol terminated with ethylene oxide groups and containing approximately 70 percent primary OH groups (hydroxyl number 5~.3, iodine number 0139), 500 parts of a polyester diol of adipic acid reacted with 1, 4-butanediol having a hydroxyl number of 54.8, 104.6 parts of 1,4-butanediol, 452 parts of 4,4'-diphenylmethane diisocyanate (flakes), 10 parts of ~Stabaxol I (hy~rolysis stabilizer by Bayer~
In this example, the NCO/OH ratio is 1.07:1.
Comparison Example A~ The NCO/OH ratio was changed by changinq the amount of chain extender used without changing the amounts of polyol and diisocyanate components.
115.2 parts of 1,4-butanediol w~re used.
The NCO/OH ratio i~ 1.00:1.
~LiL3~
Table I
Comparison Example 1 Example NGO~OH Ratio 1.07:1 1.00:1 Physical Properties Hardness [Shore A/D~85/32 84/27 Tear Strength [N/mm2] 40 10 (DIN 53 504) Breaking Elongation [~] 650 550 (DIN 53 504) Graves Tear Strength ~N/mm] 5~ 40 (DIN 53 515~
Wear ~DIN 53 516) [mm3] 80 300 10 Specific Weight [g/cm3] 1.16 1.16 ~DIN 53 550) Freezing Temperature [~C] -55 --(DIN 53 513) A~ter storage in water at 80C for 21 days:
Tear Strength [N/mm2~ 18 --Elongation [~] 300 --
Vieweg and El. Hoechtlen, Carl Hanser Pl:blishers, Munich, 1966 Pages 20b and the following.
In spite of the advantages concerning their mechani-cal ~tability and their wear behavior, polyurethane elastomers ~13~
based on polyester p~lyols also have some very negative properties. These products, unless stabilized or improved by suitable additives, are sensi~ive to hydrolytic decomposition or infestation and destruction by micro organisms. Further-more, the flexibility of these elastomers, particularly the hard formulations, leaves something to be desired at tempera-tures below ~reezing. For example, applications at low temperatures are not feasible because of the relatiYely high solidification temperatures of the elastomers which in turn depend on the chemical compositions and their hardness.
Compared with this, polyurethane elastomers based on polytetrahydrofurans have the advantage of greater hydrolysis resistance, resistance to micro organisms and flexibility even at low temperatures to minus 50C and below.
A disadvantage, howeverr is that the mechanical properties of these products can be varied only within narrow limits because in principle only the molecular weight of the polytetrahydrofuran can be changed and that the production oosts of these products are relatively high.
It seemed appropriate to also use other poly-oxyalkylene glycols for the manufacture of polyurethane elastomers instead of the hydroxyl group-containing polytetra-hydrofurans. In many cases, howeYer, the reaction of polyoxy-alkylene glycols with polyisocyanates in the one-stage process takes place so slowly, even in the presence of catalysts, that an economically desirable process is not feasible. Only by means of polyoxyalkylene polyol polyisocyanate prepolymers, ~376~1~
which are ~ubsequently reacted with ~hain extenders, can the desired end product be obtained in a reas~nable and control-1 able manne r .
Using the prepolymer stage, however, means a rela-tively higher equipment requirement compared with the ~ingle-~tage process. In addition to the already required storage capacities for the p~lyoxyalkylene polyol and the polyiso-cyanate, the prepolymer process, contrary to the single-step process, requires equipment for the manufacture of the pre-polymer, and sufficient storage capacity for the completedprepolymer, while the formulation is being adjusted which is generally required for reliable processing into a high-quality elastomer. Furthermore, the requirements of mixing e~uipment for the reaction of the prepolymer and chain extenders under certain circumstances can vary greatly due to their viscosity and the quantities employed. It is also known that pure polyether polyols can be stored for an extended period of time contrary to isocyanate prepolymers which, at temperatures up to 80-C, are difficult to ~tore and can only, under certain circumstances, with the aid of 6uitable a~ditives, be main-tained constant with respect to the viscosity and reactivity for a sufficiently long period of time~
The purpose of this invention is to manufacture from inexpensive, easily obtainable raw materialx empl~ying a technically ~imple process, polyurethane elastomers having high resistance against micro organis~s and good mechanical 1:~3~71 i9~
properties, particularly at temperatures below the freezing point.
Surprisingl~, it was found that thermoplastically, easily processable polyurethane elastomers with good mechanical properties and excellent hydrolysis and microbe-resistance can be produced from higher molecular weight polyoxyalkylene polyols, quickly and in a simple manner in a single-stage reaction. Polyoxyalkylene polyols having primary hydroxyl groups are reacted either alone or in mixtures, with certain polyether polyols or polyester polyols, with polyisocyanates, particularly aromatic diisocyanates, chain extenders, possibly in the presence of catalysts, or other additives. The accurate maintenance of a narrow range of the WCO/OH ratio is the determining factor for obtaining good mechanical properties. Surprisingly, this is successful in spite of the known, hi.gh monofunctional contents of such polyether diols which may amount to 10 percent by weight and more.
In particular the present invention provides hydrolysis and microbe-resistant thermoplasticly processable polyurethane elastomers having hardness degrees of 60 Shore A
to 75 Shore D which are obtained by a one shot process comprising reacting A) primarily linear polyether polyols having molecular weights of 500 to 10,000 in which at least 50 percent of the OH groups are primary hydroxyl groups or B) mixtures of such polyether polyols ~A) with hydroxyl group containing polytetrahydrofuran and/or primarily linear polyester polyols, C) low molecular weight linear chain extenders, and D~ organic diisocyanates wherein the ratio of NCO groups to hydroxyl groups of compo-,;s..~.
~L376~
nents (A) or ~B) and (C) is 1005:1 to 1.08:1.
In another aspect the present invention provides a one shot process for the manufacture of hydrolysis and microbe-resistant thermoplasti.cally processable polyurethane elastomers havlng hardness degrees of 60 Shore A to 75 Shore D wherein A) primarily linear polyether polyols with molecular weights of 500 to 10,000 in which at least 50 pèrcent of the OH groups are primary hydroxyl groups or s) mixtures of such polyether polyols (A) with hydroxyl group containing polytetrahydrofuran and/or primarily linear polyester polyols C) low molecular linear chain exterders and D) organic diisocyanates are reacted at temperatures of 20 to 250C is such quantities -that the ratio of the NCO groups to the hydroxyl groups of components (A) or (B) and (C) is 1.05 to 1.08:'.
Description of the Preferxed Embodiments Hydrolysis- and microbe-resistant thermoplastically - 20 processable polyurethane elastomers having hardness degrees of 60 Shore A to 75 Shore D are-obtained by the reaction of A) primarily linear polyether polyols having molecular weights of 500 to 10,000 in which at least 50 percent of the 0~ groups are primary hydroxyl groups or, .
: ~.
~ a -7~
B) mixtures of such polyether polyols (A) with hydroxyl group-containing polytetrah~drofurans and/or primarily linear polyester polyols, C~ low molecular, linear chain extenders, and D) organic diisocyanatesg These raw materials are reacted employing the one-shot process, possibly in the presence of catalysts and auxiliaries, in such quantities that the ratio of NCO groups to hydroxyl groups in the starting components (A) or ~B) and ~C) is 1.05:1 to 1.08:1.
The molar ratios between polyether polyol (A) or the mixtures (B) of polyether polyol (A) and polytetrahydrofuran and/or polyester polyol and chain extender (C) may be varied within ~ide limits. Depending upon the desired hardness of the polyurethane elastomer, the ratio of polyol to chain extender can vary from about 1.0~ D5 to approximately 1.0:1.0, preferably from 1~0: 09 08 to 1.0;0.8. The quantity of the chain extender employed is also a function o the molecular weight of the polyether polyol ~A) or the mixture (B~.
Those polyethers polyols contemplated for the manufa~ture of the polyurethane elastomers according to this invention, are those polyether pvlyols (A~ which are primarily linear, that is di~unctional, of molecular weight ranges of 500 to 10~000r preferably o~ 600 to 6,000, and in which at least 50 percent, preferably 60 to 80 percent, of the OH
groups are primary hydroxyl groups~ Particularly suited a~
polyether polyols are the condensation products of ethylene ~5-. ~3~
oxide, propylene oxide, 1,2 butylene oxide, tetrahydrofuran, epichlorohydrin~ and styrene oxide with s~arter molecules, preferably those starter molecules containing 2 active hydrogen atoms. Suitable starter molecules include: water, N-alkyldiethanolamines having 1 to 4 carbon atoms in the alkyl radi~al such as N-methyl-diethanolamine and preferably, aliphatic diol~, parti~ularly those having 2 to 6 carbon atoms su~h as ethylene glycol, propylene slycol, 1,4-butanediol and 1,6-hexanediol. Mixtures of starter molecules may al o be used if desired.
For the manufacture of the polyether polyols (A~, the alkylene oxides may be reacted in mixtures, in blocks, or ~equentially in blocks with the stipulation that the end product contains at least 50 percent primary hydroxyl groups.
Preferably used are those polyether polyols of propylene oxide and ethylene oxide where at least part of the ethylene oxide i~ arranged as a terminal block.
Such polyether polyols may be obtained, for instance, by initially condensing the propylene oxide with the starter molecules followed by the addition of ethylene oxide~ or by initially condensing all of the propylene oxide as a mixture with part of the ethylene oxide and subseguently condensing the remainder of the ethylene oxide~ or by initially condens-ing past of the ethylene oxide~ then the entire propylene oxide, followed by condensing the re~t of the ethylene oxide with the starter moleculeO
. ~3769~
Polypropylene glycols which have been terminated with tetrahydrofurans have proven to wor~ well ~nd are there fore preferred.
The polyether polyols (A) may be used individually as well as in mixture~. They may be mixed with hydroxyl group-containing polytetrahydrofurans having molec~lar weights of 500 to 6000, preferably of 600 to 3000, and/or with primar-ily linear polyester polyols having molecular wieghts of 500 to 4500, preferably 600 to 3000. Mixtures (B) of polyether polyols (A) and hydroxyl group-con~aining polytetrahydrofurans and/or polyester polyols containing more than 50 percent by weight, preferably 60 to 99 percent by weight of polyether polyols based on the total weight of polyether polyols have proven to work particularly well.
The process for the preparation of hydroxyl group-containing polytetrahydrofurans is well known. Products produced by the polymerization of tetrahydrofuran in the presence of acetic anhydride with antimony pentachloride as a c~talyst and subsequent transesterification have proven to work particularly well~
Suitable primarily linear polyester polyols are obtained (1) by the polymerization of caprolactones, prefer-ably epsilon-caprolactone, (2) by the polycondensation of omega-hydroxy-carboxylic acids, or (3) by the reaction of aliphatic dicarboxylic acids having 4 to 6 carbon atoms, e.g~, 6uccinic acid, glutaric acid and adipic acid, with aliphatic glycols having 2 to 6 carbon atoms, such as 1,6-hexanediol~
. ~IL3~69~ -and preferably 17 4-butanediol and ethylen~ glycol . Polyester polyols preferably used for the manufacture of the poly- -urethane elastomers according to this invention include hydroxyl group-containing caprolactones and adipates of adipic acid with 1~4-bu~anediol, mixtures of i~4-butanediol and ethylene glycol, or 1,6-hexanediol in a mole ratio of 4:1 to 1:4, preferably 1:1.
The low molecular linear chain extenders employed have molecular weights of less than 500, preferably of 60 to 300. Suitable substances include aliphatic diols ~ith 2 to 12 carbon atoms and particularly, those with an even number of carbon atoms, esters of terephthalic acid with glycols having 2 to 4 carbon atoms, and hydroxyalkylene ether of hydroquinone.
Examples of these include: ethylene glycol, 1,4-butanediol, 1,6-hexanediol, terephthalic acid-bis-ethylene glycol, or 1,4-butylene diglycol and 1,4-di-(beta-hydroxyethyl)-hydro quinone with 1,4-butanediol having been proven ~o work particularly well.
Suitable organic diisocyanate~ (D~ for the manufac-ture of the polyurethane elastomers according to thi& inven-tion are cycloaliphatic, aliphatic and, preferably, aromatic diisocyanates. These include: cycloaliphatic diisocyanates ~uch as 1,4-cyclohexane diisocyanate~ 4,~'-diisocyanato di~y~lohexylmethane, or i~ophorone diisocyanate; aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate~ and aromatic diisocyanates such as diphenyl diisocyanate, m- or p-phenylene diîsocyanate, 2,4- ana 2,6-toluene diisocyanate or ~ ~376g~
their i~omer mixtures; ~,2'-, 4,47-~ 2,~ diphenylmethane diisocyanate or their ~omer mixtures, andlpreferably, 4.4'~
diphenylmethane dii~ocyanate.
As previously mentioned9 lt i~ an imp~rtant facet of thi~ $nvention that, in order to obtain polyurethane elastomer~
with good mechanical properties, ~he ~arting camponent~ ~A~
to (D) are reac~ed in a narrow NCO/O~ ratio. According to the invention~ the st~rting c~mponents are reacted in such quanti ties that the ratio of NCO groups of the diisocyanates ~D) to the ~um of the hydroxyl groups of the component (A~ or (B) and (C) i~ 1.05:1 to 1.08:1, preferably 1~07:1. The ratio of NCO
to OH groups must be maintained in spi te of the varying ratios of components (A) or (~). A slight drop below this NCO/OH
ratio can very ~uickly result ~n crumbly, mechanically worth less materials. ~xceeding ~he value!s can result in products which have unstable storage properti.es which are partially insoluble in solven~s, which cont~in swelling materials and which are thus difficult or no longer processable in a thermo-plastic manner because of he vi~cosity which "after develops"
20 over an extended period of time.
The polyurethane elastomers according to thi~ inven-tion can be produced according to the one-shot process, in the presence of catalyst~, in a batch-type manner, ~r prefer-ably in a continuous manner wherein the reaction mixture i~
carried on ~ continuous circulating band after ~uitable metering and mixing of the ~tarting components at tempera~ures of 20 to 150-C, preferably S0 to 130~C~ On the circulating _g_ ~..
. ~37~9~
band, the reaction mixture goes ~hrough a temperature profile, first to 100 ~o 250C, then dropping to 20~C to ~00C as a result of exothermal reaction. ~he reaction mixture is removed and urther proeessed after solidifying in plates, or it can be ~ed directly to a conveyor granulator as an endless thick plate.
In addition to this, the single-stage reaction may also be conducted in a ~o called reaction extruder.
Suitable catalysts which accelerate the reaction between the NC0 groups of the isocyanates and the hydroxyl groups of components (A) or (B) and ~C) are the tertiary amines well known to those skilled in the art. These include triethylamine, dimethylcyclohexylamine, N-methylmorpholin~r N,NI-dimethylpyrazine, diazabicyclo~-(2,2,2)-octane and similar materials as well as organic metal compoullds such as titanic esters, iron compounds such as iron acetylacetonate, tin diacetate, tin dioctoate, tin dilaurate, or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetatet dibutyltin dilaurate, or ~imilar materials. m e 20 catalysts are normally used in quantities of 0.001 to û.l p~rt per 100 parts of polyether polyols ~A) or mixture (B~ If desired, the catalyst can be eliminated.
In addition to catalysts, other additives may also be incorporated in the reaction components without detriment~
These incl~de inhibitorst stabilizers with respect to light, heat or discolora'Lion, dye~, color pigments, inorganic and orgarlic filler~.
~37~9~
The polyurethane elastomers produced according to the instant invention have hardness ~egrees of 60 Shore A to 75 ~hore D~ show good hydrolysis resistance, very good resist-ance to the infestation of micro organisms and have excellent mechanical properties.
Depending upon their chemical compo~ition, the p~lyurethane elastomers are transparent or opaque and generally have a high crystallini~y~ They can, therefore, be processed correspondingly well into, hoses, hollow parts, foils, and melt-coatings according to the collander, spray injection~
extrusion, and blowing processes. ~hey are soluble in ~uit-able organic solvents such as dimethyl formamide without undergoing swelling and thus, suitable for textile coatingsO
As a result of the very pronounced incompatibility between the rigid segment and the amorphous range, unusually low freezing temperatures of minus 50C and below, and good ther~al stabilities of 150C and above are obtained even with high hardness degrees of, for instance, 63 Shore D.
The following Examples are intended to illustrate the nature o~ ~he inYention. Unless otherwise stated, the parts and percentages are by weight.
1~--. ~IL37~
Example 1 General Process Inst_uctions:
A stipulated am~unt of a polyoxyalkylene diol with a polypropylene oxide chain and terminal primary hydroxyl groups or a mixture of such a polyoxyalkylene diol with othex polyols and polytetrahydrofuran diols or polyester polyols is heated - to 80 to 120C while being stirred vigorously. An amount of 1,4-butanediol corresponding with the desired NCO/OH ratio and required for the desired degree of hardness of the resulting polyurethane elastomer is added. As the chain extender is added the temperature of the mixture drops by approximately 20C. After mixing for approximately one minute, the cal~
~ulated ~uantity of 4,4'-diphenylmethane diisocyanate in the form of flakes is added whereupon the temperature of the re-action mass initially drops to about 40 to 60C and sub-sequently quickly begins to increase and can reach tempera-tures up to 180~C and more within a few minutes. Before the reaction mixture solidifies, approximately upon passing ~hrough the 100~C mark, a ~hin layer of ~.he reaction mass is poured in~o molds which are heated to 100 to 130C and where the exothermal polyaddition reaction is completed with~n a sh~rt period of time. The unmolded panels are tempered at B0 to 100C ~or 15 hours, are subsequently crushed and are sprayed onto samples.
Liquid 4,4'-diphenylmethane diisocyanate is pre~er-ably employed in a continuous process. 5uitable catalysts and stabilizexs may also be employedl ~37~
An elas~omer was prepared via the general process instructions empls~ying the following:
5ûO parts of a pc lypropylene glycol terminated with ethylene oxide groups and containing approximately 70 percent primary OH groups (hydroxyl number 5~.3, iodine number 0139), 500 parts of a polyester diol of adipic acid reacted with 1, 4-butanediol having a hydroxyl number of 54.8, 104.6 parts of 1,4-butanediol, 452 parts of 4,4'-diphenylmethane diisocyanate (flakes), 10 parts of ~Stabaxol I (hy~rolysis stabilizer by Bayer~
In this example, the NCO/OH ratio is 1.07:1.
Comparison Example A~ The NCO/OH ratio was changed by changinq the amount of chain extender used without changing the amounts of polyol and diisocyanate components.
115.2 parts of 1,4-butanediol w~re used.
The NCO/OH ratio i~ 1.00:1.
~LiL3~
Table I
Comparison Example 1 Example NGO~OH Ratio 1.07:1 1.00:1 Physical Properties Hardness [Shore A/D~85/32 84/27 Tear Strength [N/mm2] 40 10 (DIN 53 504) Breaking Elongation [~] 650 550 (DIN 53 504) Graves Tear Strength ~N/mm] 5~ 40 (DIN 53 515~
Wear ~DIN 53 516) [mm3] 80 300 10 Specific Weight [g/cm3] 1.16 1.16 ~DIN 53 550) Freezing Temperature [~C] -55 --(DIN 53 513) A~ter storage in water at 80C for 21 days:
Tear Strength [N/mm2~ 18 --Elongation [~] 300 --
3~
xamples 2-_ The procedure sf Example 1 was followed to prepare elastomers employing the fol~owing components.
Example 2 1,000 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi-mately 70 percen~ primary OH groups (hydroxyl number 59.3 and iodine number ~.39) ~:~
10358.8 parts of 1,4-butanediol 1,207 parts of 4,4'-diphenylmethane diisocyanate The NCO/OH ratio is 1.07:1 Example 3 500 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi-mately 70 percent primary OH groups (hydroxyl number 59~3, iodine number 0O39) 500 part~ of a polyester polyol ~f adipic a~id 2D reacted with equimolar quantities vf ethylene glycol and 1,4 butanediol with a hydroxyl number o~ 54.1 357.9 parts of 1~4-butanediol 1,201 parts of 4,4'-diphenylmethane diisocyanate part~ o f ~t abaxol X
The NCO/OH ra~io is 1.07:1.
~3'76~
Example 4 1,000 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi~
mately 70 percent primary OH groups ~hydroxyl number 28.0 and 0.6 mval/g unsaturated groups) 325,1 parts of 1,4~butanediol 1,037 parts 4,4'-diphenylmethane diisocyanate The NCO~OH ratio is 1.07:1.
~
500 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi-mately 70 percent primarv hydroxyl groups (hydroxyl number 2B. O and D . 6 mval/g unsaturated groups~
500 parts of a polyester polyol of adipic acid reacted with equimolar quantities of ethylene glycol and 1,4-butanediol with a hydroxyl number of 54.1 32S.1 part. 1,4-butanediol 1,066 parts 4,4' diphenylmethane diisocyanate The NCO/OH ratio i~ 1.07:1.
~37~
U~
;~ o ~ ~ o ~ ~ In o t~ ~ In o o ~ ~`I ~ N O
~3 ~ ~ ~ o I ~, 1~
1~
O J~
~ C~
_~ ~ ~7 0 ~C: I` O O c~
Q ~n ~ O O O ~ ~9 ~ O
E~ ~ ~ ~
Q~J
~3 ~J
QJ J~
aJ O
h !.
U~
~--I
_~ I` n oo o ~ o C:~ o O
-- ' I ~ ~1 I
~C
5~
~ ~C
,~ u~ In O O O 0~ 0 ~ O E
t~ u~ 1~ 0 13 ~ ,~ _ . I el~G Q~
~a I _ ~ ~ ~
H ~1 0 ~_ ~Q
a~ ._ _~ ~ Q~
al ~ u~
E~ ~
Q~ ~2 ~ ~ ~ ~ ~ C
~ O
~ e ~ ~ t~3~ dP ~ ~
~ o o o ~
_ ~ ~ o o In u~
,., _ ~ O U~
Z U~
O Z ~ ~ o ~ o a ~ ~
C ~ O
Z O Cl~ Dx oq C ~ "~li:l ~J ~ ~I c ~ ~ ~ U~ .C ~ ~ O ~
R V o u~ o~ ~:
~4 ~ ~ 1 P~ C li3 1~ z ~ E~ ~ C W
_ID~ ~V
~ to ~ e Q ~ C LO J- IC 0 ~1 r) N~1 .C ~
E~ nE~ O
~13~
Examples 6 and 7 The procedure of Example 1 was used to prepare the pr~ducts of Examples 6 and 7 employing the following components.
ltOOO parts of a polypropylene glycol terminated with ethylene oxide and containing approximately 70 percent primary hyclroxyl groups ~hydroxyl number 109 and iodine number 0.05) 150 parts 1,4-butanediol 695 parts 4,4'-diphenylmethane diisocyanate The NCO~OH ratio is 1.05:1.
Example 7 1,000 parts of a polypropylene glycol terminated with ethylene oxide and containing approximately 70 percent primary hydroxyl groups (hydroxyl number 019 and iodine number 0.05) 145.5 parts 1,4-butanediol 695 parts 4,4'-diphenylmethane diisocyanate The NCO/OH ratio i~ 1.07:10 -~8 . ~L3~
r-~ o ~ u7 In n ~ o a) - ~ ~ ~ ~ a~ ~D N c~ ei~
~1 1` ~ U~
..
aJ
~ .~ :
~ o Uf~ ~ ~ O h 1~5 aJ . ~ ~ D ~ ~ N Q
Q ~
. SD -- ~
~C
~e c o O o H r_ _ U) _ lli Q~
1 E J~ O
O ~ o s~
E ~ C) ~ ~ C
U~ Z A Z ~ ~ ~
lu ~ O
E~
~ s a~
o u~ ~nt3 ~ J~
o o n z ~
o Z :~ ~
H Q ~ Cl ~J Ul O
U'~ S ~ ~ J~
C ~ ~ ~J ~ C
a~ a!; o g~ c~ 3 3; 0 ~ h O
~ ~ .r~ 5 ~ ~ li3 0 10 JJ f~ e ~ , ~ ~ ~ p Q~ ~ ~ u~ ~ O
.c O O ~ ~ ~ ~ O
.,, ~ ,, " u~ ~ ,, ~ r æ
æ t, ~ o ~ ~ ~ ~ C110 J~ ~ V
CJ al~ 0 U~ ~1 M ~ rt 111 61 V~ ~ ~ ~ ~ h 1~1 ~ o ~ I qJ SU
P~ ~ m - _1 9--
xamples 2-_ The procedure sf Example 1 was followed to prepare elastomers employing the fol~owing components.
Example 2 1,000 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi-mately 70 percen~ primary OH groups (hydroxyl number 59.3 and iodine number ~.39) ~:~
10358.8 parts of 1,4-butanediol 1,207 parts of 4,4'-diphenylmethane diisocyanate The NCO/OH ratio is 1.07:1 Example 3 500 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi-mately 70 percent primary OH groups (hydroxyl number 59~3, iodine number 0O39) 500 part~ of a polyester polyol ~f adipic a~id 2D reacted with equimolar quantities vf ethylene glycol and 1,4 butanediol with a hydroxyl number o~ 54.1 357.9 parts of 1~4-butanediol 1,201 parts of 4,4'-diphenylmethane diisocyanate part~ o f ~t abaxol X
The NCO/OH ra~io is 1.07:1.
~3'76~
Example 4 1,000 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi~
mately 70 percent primary OH groups ~hydroxyl number 28.0 and 0.6 mval/g unsaturated groups) 325,1 parts of 1,4~butanediol 1,037 parts 4,4'-diphenylmethane diisocyanate The NCO~OH ratio is 1.07:1.
~
500 parts of a polypropylene glycol terminated with ethylene oxide and containing approxi-mately 70 percent primarv hydroxyl groups (hydroxyl number 2B. O and D . 6 mval/g unsaturated groups~
500 parts of a polyester polyol of adipic acid reacted with equimolar quantities of ethylene glycol and 1,4-butanediol with a hydroxyl number of 54.1 32S.1 part. 1,4-butanediol 1,066 parts 4,4' diphenylmethane diisocyanate The NCO/OH ratio i~ 1.07:1.
~37~
U~
;~ o ~ ~ o ~ ~ In o t~ ~ In o o ~ ~`I ~ N O
~3 ~ ~ ~ o I ~, 1~
1~
O J~
~ C~
_~ ~ ~7 0 ~C: I` O O c~
Q ~n ~ O O O ~ ~9 ~ O
E~ ~ ~ ~
Q~J
~3 ~J
QJ J~
aJ O
h !.
U~
~--I
_~ I` n oo o ~ o C:~ o O
-- ' I ~ ~1 I
~C
5~
~ ~C
,~ u~ In O O O 0~ 0 ~ O E
t~ u~ 1~ 0 13 ~ ,~ _ . I el~G Q~
~a I _ ~ ~ ~
H ~1 0 ~_ ~Q
a~ ._ _~ ~ Q~
al ~ u~
E~ ~
Q~ ~2 ~ ~ ~ ~ ~ C
~ O
~ e ~ ~ t~3~ dP ~ ~
~ o o o ~
_ ~ ~ o o In u~
,., _ ~ O U~
Z U~
O Z ~ ~ o ~ o a ~ ~
C ~ O
Z O Cl~ Dx oq C ~ "~li:l ~J ~ ~I c ~ ~ ~ U~ .C ~ ~ O ~
R V o u~ o~ ~:
~4 ~ ~ 1 P~ C li3 1~ z ~ E~ ~ C W
_ID~ ~V
~ to ~ e Q ~ C LO J- IC 0 ~1 r) N~1 .C ~
E~ nE~ O
~13~
Examples 6 and 7 The procedure of Example 1 was used to prepare the pr~ducts of Examples 6 and 7 employing the following components.
ltOOO parts of a polypropylene glycol terminated with ethylene oxide and containing approximately 70 percent primary hyclroxyl groups ~hydroxyl number 109 and iodine number 0.05) 150 parts 1,4-butanediol 695 parts 4,4'-diphenylmethane diisocyanate The NCO~OH ratio is 1.05:1.
Example 7 1,000 parts of a polypropylene glycol terminated with ethylene oxide and containing approximately 70 percent primary hydroxyl groups (hydroxyl number 019 and iodine number 0.05) 145.5 parts 1,4-butanediol 695 parts 4,4'-diphenylmethane diisocyanate The NCO/OH ratio i~ 1.07:10 -~8 . ~L3~
r-~ o ~ u7 In n ~ o a) - ~ ~ ~ ~ a~ ~D N c~ ei~
~1 1` ~ U~
..
aJ
~ .~ :
~ o Uf~ ~ ~ O h 1~5 aJ . ~ ~ D ~ ~ N Q
Q ~
. SD -- ~
~C
~e c o O o H r_ _ U) _ lli Q~
1 E J~ O
O ~ o s~
E ~ C) ~ ~ C
U~ Z A Z ~ ~ ~
lu ~ O
E~
~ s a~
o u~ ~nt3 ~ J~
o o n z ~
o Z :~ ~
H Q ~ Cl ~J Ul O
U'~ S ~ ~ J~
C ~ ~ ~J ~ C
a~ a!; o g~ c~ 3 3; 0 ~ h O
~ ~ .r~ 5 ~ ~ li3 0 10 JJ f~ e ~ , ~ ~ ~ p Q~ ~ ~ u~ ~ O
.c O O ~ ~ ~ ~ O
.,, ~ ,, " u~ ~ ,, ~ r æ
æ t, ~ o ~ ~ ~ ~ C110 J~ ~ V
CJ al~ 0 U~ ~1 M ~ rt 111 61 V~ ~ ~ ~ ~ h 1~1 ~ o ~ I qJ SU
P~ ~ m - _1 9--
Claims (7)
1. Hydrolysis and microbe-resistant thermoplastic-ly processable polyurethane elastomers having hardness degrees of 60 Shore A to 75 Shore D which are obtained by a one shot process comprising reacting A) primarily linear polyether polyols having molecular weights of 500 to 10,000 in which at least 50 percent of the OH groups are primary hydroxyl groups or B) mixtures of such polyether polyols (A) with hydroxyl group containing polytetrahydrofuran and/or primarily linear polyester polyols, C) low molecular weight linear chain extenders, and D) organic diisocyanates, wherein the ratio of NCO groups to hydroxyl groups of compo-nents (A) or (B) and (C) is 1.05:1 to 1.08:1.
2. The polyurethane elastomers of claim 1 wherein polypropylene glycols terminated with ethylene oxide and/or tetrahydrofuran are used as the polyether polyols (A).
3. The polyurethane elastomers of claim 1 wherein the polyester polyols are selected from the group consisting of hydroxyl group-containing polycaprolactone, 1,4-butanediol adipates, 1,4-butanediol ethylene glycol adipates, and 1,4-butanediol-1,6-hexanediol adipates.
4. The polyurethane elastomers of claim 1 where-in said chain extender (C) is selected from the group consisting of ethylene glycol, 1,4-butanediol and 1,6-hexanediol.
5. The polyurethane elastomers of claim 1 wherein 1,4-butanediol is used as chain extender (C) and 4,4'-diphenylmethane diisocyanate is used as organic diisocyanate (D).
6. A one shot process for the manufacture of hydrolysis and microbe-resistant thermoplastically proces-sable polyurethane elastomers having hardness degrees of 60 Shore A to 75 Shore D wherein A) primarily linear polyether polyols with molecular weights of 500 to 10,000 in which at least 50 percent of the OH groups are primary hydroxyl groups or B) mixtures of such polyether polyols (A) with hydroxyl group containing polytetrahydrofuran and/or primarily linear polyester polyols C) low molecular linear chain extenders and D) organic diisocyanates are reacted at temperatures of 20 to 250°C in such quantities that the ratio of the NCO groups to the hydroxyl groups of components (A) or (B) and (C) is 1.05 to 1.08:1.
7. The process of claim 6 wherein the reaction is started at temperatures from 20 to 150°C and then passes through a temperature profile which initially increases to 100 to 250°C and finally drops to 100 to 20°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2850608.3 | 1978-11-22 | ||
| DE19782850608 DE2850608A1 (en) | 1978-11-22 | 1978-11-22 | Thermoplastic polyurethane elastomers for coatings and mouldings - with improved resistance to hydrolysis and microorganisms |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1137690A true CA1137690A (en) | 1982-12-14 |
Family
ID=6055324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000340275A Expired CA1137690A (en) | 1978-11-22 | 1979-11-21 | Hydrolysis and microbe-resistant thermoplastically processable polyurethane elastomers, their manufacture and use as coating materials and molded parts |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1137690A (en) |
| DE (1) | DE2850608A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632866B2 (en) | 2000-04-25 | 2003-10-14 | Bayer Aktiengesellschaft | Aliphatic thermoplastic polyurethanes and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3042558A1 (en) * | 1980-11-12 | 1982-06-24 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING COLD-FLEXIBLE, OR CELL-CONTAINING POLYURETHANE ELASTOMERS |
| DE10022848B4 (en) * | 2000-05-10 | 2004-07-15 | Bayer Ag | Molded body made of thermoplastic polyurethane with reduced fogging |
-
1978
- 1978-11-22 DE DE19782850608 patent/DE2850608A1/en not_active Withdrawn
-
1979
- 1979-11-21 CA CA000340275A patent/CA1137690A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632866B2 (en) | 2000-04-25 | 2003-10-14 | Bayer Aktiengesellschaft | Aliphatic thermoplastic polyurethanes and use thereof |
| US6706807B2 (en) | 2000-04-25 | 2004-03-16 | Bayer Aktiengesellschaft | Aliphatic thermoplastic polyurethanes and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2850608A1 (en) | 1980-06-12 |
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